Method of making organic mercury compounds



ooMPoU-Nns ming'ton, Del., a corporation of Delaware-ir'iventionijrelates kto. @the `prepara{n ionA- fof certain .types.oforganio mercury; compounds.

`'ll'hisapplication is acontinuationinpart oi my .1 Inorder totillustratom the following;exemples/faro e1 s understood :that: thoseare, illustrative; merely. and .are not tube-taken .my -inyentiom.Eomplo 1%- o ourichlordodissolved orouspoodoo :in foloohol,twenty-faremo. of. f-totraethylflood .#orozslowlytmtroduoed-,fthof wholebeine ,f wollt immediate zu; precipitation f. of i. chloride,- beeins, f#Ehe-mixture .ls-then located :on a water rpath,I forfabootftl-xirtyminutes...

copending applicationl Serial` No.v 231,159, led

y -Up-.tol thepresent,y timethe methodsoutilized in theY preparation of;organic y mercurio compounds, ofi-,they .type represented :by ethylmercurio ..oh.loride,v have .been very laborious and time .consuming.Duetogthe diculty o fproducing-these materials, ..s'uchz:.i1mercurials fare .;not; readily available, and .-arevvery expensive. Ethylmer- .curiochloride, forflexample, is generallyy preapared in eitheryofftwoyways..=l }irst, by ,treating ethyl bromide;1 with l sodium amalgam, and, gdecomposingithe; mercury diethylv -thus formed with mercurio z chloride.The; yields by this method are: very i poor, fand. the :qmethod .isA.onlyzgoiv his- -ltorical interest- The secQnd methodof preparinerethylrmercuric chloridezis bystlieuse of-thets'o calledfG'rignardreagent. This -methodrequiring, -asitwdoest'the use .of anhydrousetherginlarge V`quantities, is, a reaction .very .poorly s uitedor:large .scalesV operations,l because :of -the dangers .1 inherent .inther method.; Furthermore; vthe `final cost of4 the product obtainedyby.this .method is '.lnecessarilyvery highl i 1 My invention, therefore;has for itsl primary object the .production oforganic-:substituted-merycury compounds. from Areagents,u rhichare readily y available, and -fromwhich'. the vdesired mercury vcompounds `may be` produced inexpensively,'quickly and by avery; simple procedure. By the use. ofv my methodVdisclosed 'hereinaftB13` ethyl mercurio chloride or any other.ethyl..mercuric salt canbeprepared from lead tetraethyl,` which nowavailable in largequantities atafrelatively lowcost.

nation of ether'and' tle consequent 'dangers'f of explosion. A stillfurther object' isthe'-gelimina- I tion of costly reagents, and theexpensivev apparatuswhich have heretofore been vneces/sary' in" the thepresent'invention relates. '`Other objects will appear heleillafterf-Y.; M f i r" These objects 'are accom -cuiy saltwitlif-analkyl'-oriar'yl derivative'fof'fa tetravalent metal. 51:1.: :l Il i I'have found fthat Whena mercurio saltis. per- `mitted to reactwith'an"alkyl 'foraryl-substituted f then subjected torextraction -ina suitableextracttor., using acetoneorbenzenezas the. solvent..A The compound ofabtetravalent metal' lying1 between mercury and the alkali'- imetal'si'- in.' the f electrolItohemicalfseries; preferablyzthe'lpresencedofia ,No pplioation November 30, 1929, f, No. 410;'8631;.z .l

alkyl or aryl substituted oroorrf Compound ...is

,anyy r`Way as: limitationsof oeitotoo.. c iAn ethyl morouro ume ofWater equal to that of the alcoh itia1ly, used is then .added the Wholevis cooled, and theprecipitate "collected ori f a lt'er.` The a highdegree of purity of the V'ethyl-@ frnercuric ,.@ero@mediatori amazones@ztample 2.-;'126 thirty-three gramsI of; .mer-

' curic chloride dissolved: or suspended inv alcohol, .fifteen-.gramsof-tetramethyl lead-are-slowly introduced; the Whole being-:well agitated,vand-immediate precipitation; ofmethyl Kmercury chloride begins.'I'hefmixture isthenflieated on agwater A furtherobjectfof'myinyentionisth elmiiequalsto -that of the: alcohol initially?used1 is thenadded. v'Iheyrhoie is cooled andthe precipitate5 collected.on apiilter; The precipitate,,when obtained-,; as; indicated in Example111,1' shows; ja :,meltingz point of :1723C.; which. indicates a-,highproduction of compounds such as' those A tol which chloride are added,and,t l 1e Wholeboiledtorone; hour. At the end offthattimeth mixture 'iscoold'and"the"s'olidcollected'on a lter. It is .phenyl mercurio.chloride is thus extracted in; so-

ven, attriti-@worte lution, and may be obtained by evaporation of asolvent. The melting point of a phenyl mercurio chloride thus obtainedis 252 C., indicating a. very high degree of purity. The probableequation is:

(cansa mammie v como @awsome-ngel Example 4.-To thirty-two grams oftri-ethyl lead chloride suspended or dissolved in alcohol twenty-sevengrams of meroux'icliloridemreadded. The whole is boiled for thirtyminutes,-an'd the ethyl mercurio chloride is dsolated in .the mannerindicated in Example ;1.` equation is:

Example 5.-To a solution of twentytwo'nam 2o of mercuric chloride in 400c c. of ethyl alcohol, *m5 @gr-ams kof A-tin ctetraphenyl 'are cadded.tis 'no'appreciable' reaction infthe cold, but =upon warming the mixturea vigorous reaction com Yn'iences. and Vmay lbe Vi'zompleted by boilinghthe *mixture-from .thirty toiortyminutes. mix- `ture lis i then andlthe precipitate -eolleeted l-erra-iilte'l'. 1Fromsthef-tltratee42further quantity of the material may be obtained by-ftheaddition"tfwaten 'The melting-point ci the phenyl-mer In.imcuriclehlorideithusfobtainedlis-about- 245fC.,-and the vaddition'of pureAphenyl h'mercury 'f chloride Vfto `-t'his material doesnot#depress-themeltingfpoint pf'thelatter. The yield-'indicates thatallffour of fthemhenylf taken orf the Atin rand 'a'.ttaehed `to fthemercury. lpmbable -fequa- "tionis:

Ezample1-'6.To afsolutlon -of ftlfty-tourlgrams 'flmercuricchlorideinllcsc. 'of-"ethyl-Jalcohol, -twelve 'gmms of itetraethyl itinfis If the sslution is bolledffor about 'two chours :audit-he-aicoiiolic solution thenv poured Uinto wwater, fthe ethyl chloride'can'be flteredf off. 'The @yield isquite good'an'flfthefpurity'of :the:product f-very'high.

'fInfthis` reactionthe ethyl; groups :oai-moti be re- :moved lcompletely 'fby fboiling 1 mercurio fchlorflfde lwithltetraethylftinfin'alcohol. `iForithisvreason L'50 theprobable.equati0ns..cannotibe,given. I

Example 7,-To a solution of sixty-three grams of fmercmic acetate 1=200'c.-c. -of rglm-iial :acetic Laci'd, twelve :grams `t:of tetraethiylAtin areJ added, 'and-fthe `'solution -boilediforsabouti-twenty minutes.

A=55 There Eis'tiiusobtained a solution fof lethylmerffcuric-acetatefwhichfcanibexreadliy-iiemonstrated fbry Fthe use:of -:'sodium* hydmxide on -a test1 portion ofthelsolution;sodium'hydroxide-C indi- 1`catesthatfnomorefmercurici ionsassucln-arefree s60 `inf-'the solution. lEthyl:mercuricnacetate-canfbe#easily-"converted into themore insoiublerchloride fbyfpouringfthe-solution fintovwaterfandfatreating :with t a r-cicentrated solution.of m00 1 grams .lof fxsddium 'chloride l'his'last' stepis thetusualvre- 55 action foreonverting organic-.mercury faoetates into .organicmercury chlorides. -fA L-heafy Jprecipitate of ethyl mercuric chlorideseparates out yianrl *may be rliltere'd The -probable -equaeitioniis:

.Bn (02H5) 4;;:4Hg CQCQCHs ).z

..4CaHaHg'QCQCH1fl-'JSI1 CQCQCIL) 4 mietpmmbie ethyl may be added, andthe solution boiled for twenty minutes. The solution thus obtained maybe converted, as in Example '7, by dilution with water and treatmentwith sodium chloride. A

White precipitate of ethyl mercurio chloride is 5 flows:

.It is, of course, understood that various modi- ?.Ticationsmaybentroduced into this method without departing in any way from thespirit of myiimntion. Thus, while I have shown that mercuric chloridemay be treated with tetraethyl lead ini'thefpresencefofaalcoholsanda'precipitate of --eth-yl mercuric f chloride .-@btained ltherefrom,iinstead of mercurio "chloride :an-y suitable afmereur-ic usalt ssuchlas =other :mercurio lhali'des `:and

other inorganic mercurio compoundsfmaybeuemplayed `nori-isstheinvention'limitedato inorganic -\coxnpoun'ds for 1 organic ffderivatives:of --mercui-ly, such as :mercurio :acetata V may :readily be Asiindicated in=-the.:examp1es rabove,z it -is --possible to use mercuricacetateior other -or- `@anic or inorganic f mercuitlcs salts 'fin lieu.fof :the chloride; or, tomploy other=solvents thanualco- "hol or-glacia1aceticracidfor'.theemercuryasalt, suchfas benzene or lacetone;butyricuor:propionlc Vacidmn evenfmter .in-some casesialthoughffnatdually,r`certain solvents are :more .suitablei.than 'others 'linstead 1- ofrftetraethyl ulead, other .falkyl or aryl compounds '.mayfbe fused. Thus`A`.tetraphenyl lead-Jortetmcyclohexyl leaidfmay bezemkfplflayed. i-No,l1-is .itnecessaryforirtheupurposesnof rmy invention :that salllfournit .the :valenciessof ftetravalent fmetal fbe .-satistled fby:alkyl :or 1 aryl wadioals; for sexample, .tri-ethyl `,lead=ehilorideror trif-'phenylflead acetate mayibeemployed. 'r1-lead is not1-the -only f metal which `emayibe :utilized-I for fthe Vpurpose of :mylinvention, axinasmuch .las .1t-in compounds may be used,itibeingmnlymecessary that `the l-metal :used be ttetravaient :and lie'.abetweenmercurynand thealllaliwmetafls'. inzthe elecftroehem-icalseries -'rhe @yield :ordinarily `fin-50 x:creasesifthefreaction-mixturevbe agitatedmhile beingheatedan'dfthevreactionitemperature:may varyaccording-to thefnature ofrthesolventuused, *being,-effcoursefllower `wl-ierea more `volatilessol-.vent is employed.

I Wish it jto be;1.n'iderstood` thatfI-domot desire to belimitedl to'the exactsubstances-proportions Qnsequencc of .operations describedheretofore, .f or.obvieusmodiiicationswll OQCurtO ai Personskilleldintheart.

. ,Li/A ,process of ,promising -Organic mercury @compounds .whichcomprises. .heating amercllry gsaltmithnanfallgyl ,comnoundbftetravalentlead in the presence of a solvent.

A precesszeflprodueine organismercury-.com--nonndsmriaiehfcenwriseslheatins armen-niveau @with an faryl compoundfz-Qf tetra'valent .lead :in

the presence of a solvent.

:KS-Agnltoeessaofnmdueing mercurymhenyhchlo- :ride .which comprises.fhtmg-fmereuric chloride:withatetraphenylleadpinethe.presencefoialcohoL ,.A. ,fA- processoproducinagrganiclmercury compnundsmhichacomprisesatatmgsmmerenricssalt'15 in the presence of a solvent with an unsubstituted hydrocarbonderivative of a tetravalent metal lying between mercury and the alkalimetals in the electro-chemical series.

5. A process of producing organic mercury compounds which comprisesheating a mercuric salt in the presence of a solvent with a tetraalkylcompound of a tetravalent metal lying between mercury and the alkalimetals in the electrochemical series.

6. A process oi producing organic mercury compounds which comprisesheating a mercuric salt with an alkyl derivative of tetravalent lead inthe presence of a solvent.

7. A process of producing organic mercury compounds which comprisesheating a mercuric salt with a tetraalkyl lead compound inthe presenceof a solvent.

8. A process of producing ethyl mercuric compounds which comprisesheating a mercuric salt with an ethyl lead compound in the presence ofVa solvent.

9. A process of producing organic mercury compounds which comprisesheating mercuric chloride with an alkyl derivative of a tetravalentmetal lying betweenmercury and the alkali metals in the electrochemicalseries in the presence of a solvent.

10. A process of producing organic mercury compounds which comprisesheating a mercuric chloride with an alkyl derivative of tetravalentlead.

11. A process of producing ethyl mercuric compounds which comprisesheating mercuric chloride with tetraethyl lead.

12. A process of producing korganic mercury compounds which comprisesheating mercuric acetate with an alkyl derivative of a tetravalent metallying between mercury and the alkali metals in the electrochemicalseries in the presence of a solvent.

13. A process of producing organic mercury compounds which comprisesheating mercuric acetate with analkyl derivative of tetravalent lead inthe presence of a solvent.

14.A process of producing an ethyl mercuric compound which comprisesheating mercuric acetate with tetraethyl lead in the presence of asolvent.

MORRIS S. KI-IARASCH.

